Insecticide and fungicide



Patented Jan. 1, 1935 msnc'rlomn AND FUNGICIDE' Theron P. Remy, LosAngeles, Calilfi, assignor The Texas Company, New York, N. Y., acorporation of Delaware No'Drawing. Application June 16, 1931 Serial No.544,926

Claims. (Cl. 167-22) This invention relates to insecticides andfungithese materials. A method that is applicable for cides and moreparticularly to insecticides and this purpose is the formation of doublecomfungicides in the form of substantially dry dusts pounds with heavymetal salts. comprising mixtures of gaseous, liquid or solid Sulfonesand sulfoxides are compounds which 5 toxic organic sulfur compounds andan active correspond to the formulae 5 powdered carrying medium. Thisinvention con- R templates the manufacture of an insecticide and SO andS0 fungicide composed essentially of an activated R R dust carrier andcertain groups of organic sulfur D V Y, d usua ly result W Organiccompounds. fides are subjected to oxidizing conditions, as in 10 Allcrude oils contain some compounds of sulfur treating the pet u fid s WSodium yp which are more or less undesirable insofar as h te d uperoxidethe general commercial use of the refined pe- Thiophene andsulfonic acids are best obtained troleum products is concerned. Duringthe procby their separation from sulfuric acid tars and l5 esses ofdistillation, cracking and refining these ud Distillation y means ofsteam is one compounds may be altered in chemical onstitumethod that isuseful for this purpose. tion, and the synthesis of new organic sulfurInsecticides and fungicides'comprising certain compounds may occur. Itis desirable to remove organic and inorganic chemicals combined with athese sulfur compounds during the refining proc d carrier are Widelyknown and used t the esses. present time. In ordinary commercialpractice, 20

A study of the sulfur compounds contained in such insecticides andfungicides take the form of petroleum reveals some of them to be highlytoxic a dry dust which is used without dilution of any to insect andfungus life. Among the more toxic kind in various types of power or handdriven sulfur compounds found in petroleum or its dedusting machines.The more finely divided these rivatives are the mercaptans, thethiophenols and dusts, the more Pronounced are their insecticidal 25thiocresols, the alkyl sulfides or thio ethers, the and fungicidalproperties. This is due to the disulfides, the thiophenes, the sulfones,the sulgreater qu y of insecticidal and fungicidal foxides and thesulfonic acids. terials capable of being adsorbed on the increased Theseorganic sulfur compounds may be sepasurface.

rated from petroleum or its derivatives or from- Too fine a state ofsubdivision of the dust car- 30 the p ducts of the cracking and refiningprocrier, however, results in material losses during the esses bywell-known chemical reactions. dusting operations caused by the Ca beingIt is known that freshly distilled naphthas conhome away by aircurrents. This is an important tain sulfur compounds of the mercaptan,thiopheconsideration when the dusting of large areas by I101 andthiocresol classes, which are readily acted airplane is contemplated. 35upon by caustic soda. This reagent is usually Organic sulfur compoundsare readily adsorbed used in the form of a solution with which theinlarge qua titi s by c tai otherwise inert -untreated naphthas arewashed, and with which terials which have the further characteristic.the organic sulfur compounds react to form the property of tenaeibllslyretaining these 40 corresponding sodium salts. By acidification ofpounds and rel a g t em O y y Slowly in 40 the separated sodium salts itis possible to bring vapor form. This is a characteristic of suchadabout their reconversion to the original, corresorbents as, carefullydehydrated fullers earths, sponding mercaptans, thiophenols andthiosilica gel, acid-treated clays, activated bauxite cresols. andactivated charcoals and carbons.

Disulfldes are produced when mercaptans are I have found that whenOrganic sulfur com- 45 subjected to the doctor-treatment. This consistspounds recovered from petroleum, from its derivprincipally in reactingthem with sodium p1um-' atives or from the products obtained by crackingbite and sulfur. Recovered mercaptans may in petroleum areusedinconjunction with any of the this manner be converted into thecorresponding enumerated adsorbents, a very superior type of fidinsecticide and fungicide results. Much greater 50 Organic sulfides arepresent as such in some quantities of the organic sulfur compounds arepetroleum distillates'andinthe products obtained capable of admixturewithout detracting from by cracking petroleum, though they may be ob-.the substantially dry character of the dust and tained more readilyfrom the tars and sludges without having recourse to too high a degreeof resulting f e-S u c acid treatment of subdivision. The relativesuperiorityofthese in- 66 secticides and fungicides may in part be dueto the fact that the toxic materials are released over a relatively longperiod of time assuring a continned toxic condition. A sudden, rapidrelease of the insecticidal and fungicidal materials, which may have adeleterious effect on the plant life, is thereby likewise averted. Inpreparing dust mixtures various methods of incorporating the organicsulfur compound or sulfur compounds with the dust carrier may be used. Iprefer to bring about this result by placing a suitable carrier of amesh which may vary over wide range but preferably of between 200 and400 mesh in a suitable mixer, such as a ball mill, and slowly adding theorganic sulfur compound or sulfur compounds while the dust carrier isbeing agitated or mixed. The percentage of sulfur compound or sulfurcompounds added to the activated carrier during this mixing operation,may

vary widely depending on the desired use to which the finished dust isto be put, and accordingly, the average percentage of sulfur compound orsulfur compounds carried in the completed dust. mixture will vary widelydepending on the intended use. The present invention, therefore is notlimited tcthe use of any specific percentages of these elements with thedust carrier.

I have impregnated activated fullers earth with very small percentagesof representative compounds of several groups of organic sulfurcompounds. As an example, a dust composed of 99.8

per cent of fullers earth of- 200 mesh and 0.2 per cent of ethylmercaptan recovered from petroleum oil was dusted on citrus trees andkilled thrips, red spiders, aphis and scale insects in various stages ofdevelopment.

The disulfides are less toxic than the members of the mercaptan series,from which they are often formed during the refining processes. Thetoxic relationship for general insect and fungus use is practically thesame. While I do not wish to limit myself to the amount of organicsulfur compound carrled by the dust medium, I have found that a mixtureof 99.5 per cent of activated fullers earth of 200 mesh with 0.5 percent of ethyl disulfide recovered during the refining of petroleumproducts will kill aphis, scale insects and many species of worms andbeetles, as well as grape leaf hopper, spiders and mites.

I claim:

1. An insecticide and fungicide in the form of a substantially dry dustwhich comprises a finely divided activated adsorbent selected from thegroup consisting of dehydratedfullers earth, acid-treated clay andsilica gel impregnated with readily vaporizable organic sulfur compoundsrecoverable from petroleum and the products of refining "the sameselected'from the group consisting of mercaptans and organic disulfides.

2. An insecticide and fungicide in the form of a substantially dry dustcomprising a finely divided activated adsorbent selected from the groupconssting of dehydrated fullers earth, acid-treated clay and silica gelimpregnated with readily vaporizable mercaptan compounds recoverablefrom petroleum and the products of refining the same.

3. An insecticide and fungicide in the form of a substantially dry dustcomprising a finely divided activated adsorbent selected from the groupconsisting of dehydrated fullers earth, acid-treated clay and silica gelimpregnated with organic disulfides recoverable from petroleum and theproducts of refining the same.

4. An insecticide and fungicide in the form of a substantially dry dustconsisting of finely divided dehydrated fullers earth impregnated withreadily vapcrizable m'ercaptans recoverable from petroleum and theproducts of refining the same.

5. An insecticide and fungicide in the form of a substantially dry dustconsisting of finely divided dehydrated fullers earth impregnated withreadily vaporizable organic disulfides recoverable from petroleum andthe products of refining the same.

THERON P. REMY.

